Methods for converting pvc to elastomers

ABSTRACT

Disclosed are methods for upcycling polyvinyl chloride (PVC) that involve the dissolving of PVC in an organic solvent; and contacting the PVC with a base, thereby providing a partially dehydrochlorinated PVC. Polymers made by the disclosed, and articles therefore, are also disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority to U.S. ProvisionalApplication No. 63/060,090, filed Aug. 2, 2020, which is incorporated byreference herein in its entirety.

BACKGROUND

PVC is the 3^(rd)-most widely produced synthetic polymer worldwide,following only polyethylene (PE) and polypropylene (PP). PVC is used ina wide variety of disposable products such as food packaging, beveragebottles, and textiles as well as in long-life products such as pipes,window frames, cable insulation, and roofing materials. This means thatthe amount of PVC waste will increase over time as the long-lifeproducts are eventually disposed. Landfilling or incineration of PVC isgenerally unfavorable due to the formation and release ofchlorine-containing compounds (e.g., HCl and organics). Mechanicalrecycling of PVC (and thermoplastics in general) typically results in“downcycling” as the process is sensitive to impurities, truncatespolymer MW, and yields a product with inferior properties compared tothe virgin material.

PVC waste is highly desirable for upcycling applications as itspropensity to undergo reactions that makes it undesirable forlandfilling are actually advantageous when performed in a controlledmanner. Under appropriate conditions, PVC can be upcycled into diverseuseful and valuable polymer materials through controlled partialdehydrochlorination followed by subsequent functionalization and/orcrosslinking. Here, the targeted products are a useful elastomers(rubber) that are chemically akin to poly(chloroprene) (trade name:Neoprene), a well-known thermally and electrically insulating waterproofrubber barrier. The similarities between the structures of PVC,poly(chloroprene), and PVC which has been partially dehydrochlorinated(DHPVC) are as follows (where n and m are integers defining the numberof repeating units, which depending on the molecular weight of thepolymer can vary from 2 to 100,000 Da or more).

where n and m are integers from 1 to 1×10⁶.

Unlike PE and PP, PVC is “activated” and is more readily susceptible toreaction, especially in the presence of acid or base. The chlorine atomson the PVC backbone are labile, leaving PVC prone todehydrochlorination, an elimination reaction that forms —(HC═CH)_(n)—“polyene” segments. Partial dehydrochlorination of PVC can be used as ameans of altering PVC properties, but if performed under uncontrolledconditions, spontaneous crosslinking and/or complete degradation canoccur. The typical degradation products include aromatic compounds(formed from cyclization of the polyene segments) and HCl (Yu, J.; etal. Thermal degradation of PVC: A review. Waste Manage. (Oxford, U. K.)2016, 48, 300-314), although these products are of low value and can beobtained more readily by other means. However, the activated nature ofPVC can be advantageous if used in a controlled manner as it yieldsunique opportunities to create value-added products from anend-of-life-product that would otherwise be disposed of.

What are needed are new ways to upcycle PVC, converting it into usefulpolymers and oligomers. New products from these upcycling methods arealso desirable. The methods and compositions disclosed herein addressthese and other needs.

SUMMARY

In accordance with the purposes of the disclosed materials, compounds,compositions, articles, devices, and methods, as embodied and broadlydescribed herein, the disclosed subject matter relates to compositionsand methods of making and using the compositions. In other aspects, thedisclosed subject matter relates to methods for upcycling polyvinylchloride (PVC). In specific aspects, disclosed are methods of partiallydehydrochlorinating PVC that comprise dissolving the PVC in an organicsolvent; and contacting the PVC with a base, thereby providing apartially dehydrochlorinated PVC. Further, disclosed are methods wherebythe partially dehydrochlorinated PVC are partially hydrogenated bycontacting the partially dehydrochlorinated PVC with hydrogen in thepresence of a hydrogenation catalyst, thereby providing a partiallyhydrogenated, dehydrochlorinated PVC. In yet further aspects, thepartially hydrogenated, dehydrochlorinated PVC can again bedehydrochlorinated by dissolving the partially hydrogenated,dehydrochlorinated PVC in a second organic solvent and adding a secondbase. Still, in further aspects, disclosed are methods whereby thepartially hydrogenated, dehydrochlorinated PVC are contacted with anucleophile substituted diene in the presence of a mild base, to providea diene substituted partially hydrogenated dehydrochlorinated PVC; andcontacting the diene substituted partially hydrogenateddehydrochlorinated PVC with a bis-dienophile. In still further aspects,disclosed are methods whereby partially dehydrochlorinated PVC andpartially hydrogenated, dehydrochlorinated PVC are contacted with sulfuror other crosslinking agents. Polymers made by the disclosed methods,and articles of the disclosed polymers are also disclosed.

Additional advantages of the disclosed subject matter will be set forthin part in the description that follows and the Figures, and in partwill be obvious from the description, or can be learned by practice ofthe aspects described below. The advantages described below will berealized and attained by means of the elements and combinationsparticularly pointed out in the appended claims. It is to be understoodthat both the foregoing general description and the following detaileddescription are exemplary and explanatory only and are not restrictive.

BRIEF DESCRIPTION OF THE FIGURES

The accompanying figures, which are incorporated in and constitute apart of this specification, illustrate several aspects described below.

FIG. 1 is a comparison of FT-IR spectra for DHPVC₆₀ (top) and H₂-DHPVC₆₀illustrating hydrogenation of alkene segments. The large peak at 3300cm⁻¹ in DHPVC₆₀ is due to residual water in the samplepost-precipitation.

DETAILED DESCRIPTION

The materials, compounds, compositions, articles, and methods describedherein may be understood more readily by reference to the followingdetailed description of specific aspects of the disclosed subject matterand the Examples and Figures included therein.

Before the present materials, compounds, compositions, and methods aredisclosed and described, it is to be understood that the aspectsdescribed below are not limited to specific synthetic methods orspecific reagents, as such may, of course, vary. It is also to beunderstood that the terminology used herein is for the purpose ofdescribing particular aspects only and is not intended to be limiting.

Also, throughout this specification, various publications arereferenced. The disclosures of these publications in their entiretiesare hereby incorporated by reference into this application in order tomore fully describe the state of the art to which the disclosed matterpertains. The references disclosed are also individually andspecifically incorporated by reference herein for the material containedin them that is discussed in the sentence in which the reference isrelied upon.

General Definitions

In this specification and in the claims that follow, reference will bemade to a number of terms, which shall be defined to have the followingmeanings:

Throughout the description and claims of this specification the word“comprise” and other forms of the word, such as “comprising” and“comprises,” means including but not limited to, and is not intended toexclude, for example, other additives, components, integers, or steps.

As used in the description and the appended claims, the singular forms“a,” “an,” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “a composition”includes mixtures of two or more such compositions, reference to “thecompound” includes mixtures of two or more such compounds, reference to“an agent” includes mixture of two or more such agents, and the like.

“Optional” or “optionally” means that the subsequently described eventor circumstance can or cannot occur, and that the description includesinstances where the event or circumstance occurs and instances where itdoes not.

Ranges can be expressed herein as from “about” one particular value,and/or to “about” another particular value. By “about” is meant within5% of the value, e.g., within 4, 3, 2, or 1% of the value. When such arange is expressed, another aspect includes from the one particularvalue and/or to the other particular value. Similarly, when values areexpressed as approximations, by use of the antecedent “about,” it willbe understood that the particular value forms another aspect. It will befurther understood that the endpoints of each of the ranges aresignificant both in relation to the other endpoint, and independently ofthe other endpoint. It is also understood that there are a number ofvalues disclosed herein, and that each value is also herein disclosed as“about” that particular value in addition to the value itself. Forexample, if the value “10” is disclosed, then “about 10” is alsodisclosed.

It is understood that throughout this specification the identifiers“first” and “second” are used solely to aid in distinguishing thevarious components and steps of the disclosed subject matter. Theidentifiers “first” and “second” are not intended to imply anyparticular order, amount, preference, or importance to the components orsteps modified by these terms.

Chemical Definitions

As used herein, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a broad aspect, thepermissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, and aromatic and nonaromaticsubstituents of organic compounds. Illustrative substituents include,for example, those described below. The permissible substituents can beone or more and the same or different for appropriate organic compounds.For purposes of this disclosure, the heteroatoms, such as nitrogen, canhave hydrogen substituents and/or any permissible substituents oforganic compounds described herein which satisfy the valences of theheteroatoms. This disclosure is not intended to be limited in any mannerby the permissible substituents of organic compounds. Also, the terms“substitution” or “substituted with” include the implicit proviso thatsuch substitution is in accordance with permitted valence of thesubstituted atom and the substituent, and that the substitution resultsin a stable compound, e.g., a compound that does not spontaneouslyundergo transformation such as by rearrangement, cyclization,elimination, etc.

“Z¹,” “Z²,” “Z³,” and “Z⁴” are used herein as generic symbols torepresent various specific substituents. These symbols can be anysubstituent, not limited to those disclosed herein, and when they aredefined to be certain substituents in one instance, they can, in anotherinstance, be defined as some other substituents.

The term “aliphatic” as used herein refers to a non-aromatic hydrocarbongroup and includes branched and unbranched, alkyl, alkenyl, or alkynylgroups.

The term “alkyl” as used herein is a branched or unbranched saturatedhydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl,tetracosyl, and the like. The alkyl group can also be substituted orunsubstituted. The alkyl group can be substituted with one or moregroups including, but not limited to, alkyl, halogenated alkyl, alkoxy,alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid,ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo,sulfonyl, sulfone, sulfoxide, or thiol, as described below.

Throughout the specification “alkyl” is generally used to refer to bothunsubstituted alkyl groups and substituted alkyl groups; however,substituted alkyl groups are also specifically referred to herein byidentifying the specific substituent(s) on the alkyl group. For example,the term “halogenated alkyl” specifically refers to an alkyl group thatis substituted with one or more halides, e.g., fluorine, chlorine,bromine, or iodine. The term “alkoxyalkyl” specifically refers to analkyl group that is substituted with one or more alkoxy groups, asdescribed below. The term “alkylamino” specifically refers to an alkylgroup that is substituted with one or more amino groups, as describedbelow, and the like. When “alkyl” is used in one instance and a specificterm such as “alkylalcohol” is used in another, it is not meant to implythat the term “alkyl” does not also refer to specific terms such as“alkylalcohol” and the like.

This practice is also used for other groups described herein. That is,while a term such as “cycloalkyl” refers to both unsubstituted andsubstituted cycloalkyl moieties, the substituted moieties can, inaddition, be specifically identified herein; for example, a particularsubstituted cycloalkyl can be referred to as, e.g., an“alkylcycloalkyl.” Similarly, a substituted alkoxy can be specificallyreferred to as, e.g., a “halogenated alkoxy,” a particular substitutedalkenyl can be, e.g., an “alkenylalcohol,” and the like. Again, thepractice of using a general term, such as “cycloalkyl,” and a specificterm, such as “alkylcycloalkyl,” is not meant to imply that the generalterm does not also include the specific term.

The term “alkoxy” as used herein is an alkyl group bound through asingle, terminal ether linkage; that is, an “alkoxy” group can bedefined as —OZ¹ where Z¹ is alkyl as defined above.

The term “alkenyl” as used herein is a hydrocarbon group of from 2 to 24carbon atoms with a structural formula containing at least onecarbon-carbon double bond. Asymmetric structures such as (Z¹Z²)C═C(Z³Z⁴)are intended to include both the E and Z isomers. This can be presumedin structural formulae herein wherein an asymmetric alkene is present,or it can be explicitly indicated by the bond symbol C═C. The alkenylgroup can be substituted with one or more groups including, but notlimited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl,heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide,or thiol, as described below.

The term “alkynyl” as used herein is a hydrocarbon group of 2 to 24carbon atoms with a structural formula containing at least onecarbon-carbon triple bond. The alkynyl group can be substituted with oneor more groups including, but not limited to, alkyl, halogenated alkyl,alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylicacid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo,sulfonyl, sulfone, sulfoxide, or thiol, as described below.

The term “aryl” as used herein is a group that contains any carbon-basedaromatic group including, but not limited to, benzene, naphthalene,phenyl, biphenyl, phenoxybenzene, and the like. The term “heteroaryl” isdefined as a group that contains an aromatic group that has at least oneheteroatom incorporated within the ring of the aromatic group. Examplesof heteroatoms include, but are not limited to, nitrogen, oxygen,sulfur, and phosphorus. The term “non-heteroaryl,” which is included inthe term “aryl,” defines a group that contains an aromatic group thatdoes not contain a heteroatom. The aryl or heteroaryl group can besubstituted or unsubstituted. The aryl or heteroaryl group can besubstituted with one or more groups including, but not limited to,alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl,aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone,nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol asdescribed herein. The term “biaryl” is a specific type of aryl group andis included in the definition of aryl. Biaryl refers to two aryl groupsthat are bound together via a fused ring structure, as in naphthalene,or are attached via one or more carbon-carbon bonds, as in biphenyl.

The term “cycloalkyl” as used herein is a non-aromatic carbon-based ringcomposed of at least three carbon atoms. Examples of cycloalkyl groupsinclude, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, etc. The term “heterocycloalkyl” is a cycloalkyl group asdefined above where at least one of the carbon atoms of the ring issubstituted with a heteroatom such as, but not limited to, nitrogen,oxygen, sulfur, or phosphorus. The cycloalkyl group and heterocycloalkylgroup can be substituted or unsubstituted. The cycloalkyl group andheterocycloalkyl group can be substituted with one or more groupsincluding, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl,heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide,or thiol as described herein.

The term “cycloalkenyl” as used herein is a non-aromatic carbon-basedring composed of at least three carbon atoms and containing at least onedouble bound, i.e., C═C. Examples of cycloalkenyl groups include, butare not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl,cyclopentadienyl, cyclohexenyl, cyclohexadienyl, and the like.

The term “heterocycloalkenyl” is a type of cycloalkenyl group as definedabove, and is included within the meaning of the term “cycloalkenyl,”where at least one of the carbon atoms of the ring is substituted with aheteroatom such as, but not limited to, nitrogen, oxygen, sulfur, orphosphorus. The cycloalkenyl group and heterocycloalkenyl group can besubstituted or unsubstituted. The cycloalkenyl group andheterocycloalkenyl group can be substituted with one or more groupsincluding, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl,heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide,or thiol as described herein.

The term “cyclic group” is used herein to refer to either aryl groups,non-aryl groups (i.e., cycloalkyl, heterocycloalkyl, cycloalkenyl, andheterocycloalkenyl groups), or both. Cyclic groups have one or more ringsystems that can be substituted or unsubstituted. A cyclic group cancontain one or more aryl groups, one or more non-aryl groups, or one ormore aryl groups and one or more non-aryl groups.

The term “aldehyde” as used herein is represented by the formula —C(O)H.Throughout this specification “C(O)” or “CO” is a short hand notationfor C═O, which is also referred to herein as a “carbonyl.”

The terms “amine” or “amino” as used herein are represented by theformula NZ¹Z², where Z¹ and Z² can each be substitution group asdescribed herein, such as hydrogen, an alkyl, halogenated alkyl,alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl,heterocycloalkyl, or heterocycloalkenyl group described above. “Amido”is —C(O)NZ¹Z².

The term “carboxylic acid” as used herein is represented by the formula—C(O)OH. A “carboxylate” or “carboxyl” group as used herein isrepresented by the formula —C(O)O⁻.

The term “ester” as used herein is represented by the formula —OC(O)Z¹or —C(O)OZ¹, where Z¹ can be an alkyl, halogenated alkyl, alkenyl,alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl,or heterocycloalkenyl group described above.

The term “ether” as used herein is represented by the formula Z¹OZ²,where Z¹ and Z² can be, independently, an alkyl, halogenated alkyl,alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl,heterocycloalkyl, or heterocycloalkenyl group described above.

The term “ketone” as used herein is represented by the formula Z¹C(O)Z²,where Z¹ and Z² can be, independently, an alkyl, halogenated alkyl,alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl,heterocycloalkyl, or heterocycloalkenyl group described above.

The term “halide” or “halogen” as used herein refers to the fluorine,chlorine, bromine, and iodine.

The term “hydroxyl” as used herein is represented by the formula —OH.

The term “nitro” as used herein is represented by the formula —NO₂.

The term “silyl” as used herein is represented by the formula —SiZ¹Z²Z³,where Z¹, Z², and Z³ can be, independently, hydrogen, alkyl, halogenatedalkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl,cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group describedabove.

The term “sulfonyl” is used herein to refer to the sulfo-oxo grouprepresented by the formula —S(O)₂Z¹, where Z¹ can be hydrogen, an alkyl,halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl,cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group describedabove.

The term “sulfonylamino” or “sulfonamide” as used herein is representedby the formula —S(O)₂NH—.

The term “thiol” as used herein is represented by the formula —SH.

The term “thio” as used herein is represented by the formula —S—.

Unless stated to the contrary, a formula with chemical bonds shown onlyas solid lines and not as wedges or dashed lines contemplates eachpossible isomer, e.g., each enantiomer, diastereomer, and meso compound,and a mixture of isomers, such as a racemic or scalemic mixture.

Reference will now be made in detail to specific aspects of thedisclosed materials, compounds, compositions, articles, and methods,examples of which are illustrated in the accompanying Examples andFigures.

Methods for Partial Dehydrochlorination of PVC

It is demonstrated herein that controlled partial dehydrochlorination ofPVC in THF using a base such as NaOH exclusively promotes elimination ofHCl from the PVC backbone, resulting in dehydrochlorinated PVC (DHPVC).A strong red-orange color is observed, indicative of conjugated polyenesegments such as those contained in (3-carotene and similar naturalproducts. The degree of dehydrochlorination can been monitored byATR/FT-IR. Substitution reactions (i.e., replacing —Cl with —OH) are notobserved under these conditions, likely given the limited solubility ofNaOH in THF. DHPVC remains soluble and stable in THF up to at leastabout 95% dehydrochlorination (forming “DHPVC₉₅”), and the DHPVCproducts are is easily recovered in high yield via precipitation inwater.

The disclosed process can start from commercial PVC (e.g., “rigid” PVCpipe, cladding, siding) of the form that could be obtained from aconcentrated waste management program focused on construction sites. Itcan also start from consumer PVC (e.g., packaging, containers, tubing).Still further, by “PVC” is also meant related chlorinated plastics suchas CPVC, CPE, and PVDC. CPVC is produced by reaction of PVC with Cl₂ gasin the presence of free radicals, with additional Cl atoms replacing aportion of the H atoms on the PVC backbone. Whereas PVC can be about 57%Cl by mass, the composition of CPVC is typically about 63-69% Cl bymass, corresponding to ˜2 Cl atoms for every 3 C atoms in the polymerbackbone. CPVC is used primarily for both cold and hot water piping asit can operate up to 93° C. (200° F.), whereas PVC is limited to 60° C.(140° F.). CPVC can also undergo dehydrochlorination reactions andbecause of the additional Cl atoms, will present some alkynefunctionalities in the backbone which can enable the formation ofdifferent value-added small molecule products/product distributions. CPEis derived from PE in a process similar to that by which CPVC isproduced from PVC. The mass of Cl in CPE is typically in the range of34-44%, meaning there is about 1 Cl atom per 4 C atoms in the CPEbackbone, although the distribution/spacing of Cl atoms is random. CPEis often blended with PVC as a softener to improve impact resistance.Thus, CPE may also be present within waste PVC that does not come frompipes and CPE can be depolymerized along with PVC.

PVDC is perhaps best known as the original formulation of Saran Wrap®(aka “cling wrap”) a widely-used household food storage product withremarkable barrier properties against water, oxygen, and aromas. PVDCdecomposes above 125° C., releasing HCl and forming polyene segmentsthat serve as activated sites for depolymerization of the polymerbackbone via ethenolysis or oxidative cleavage.

In the disclosed methods, the PVC can be cut into smaller pieces, e.g.,using a saw or shredder, and these fragments can be stirred in warm THFor other organic solvent. Upon dissolution of the PVC and any organicadditives, the inorganic additives (primarily CaCO₃) remain insolubleand can be readily removed by filtration. This CaCO₃ is generally aharmless product that could be safely disposed or perhaps reused/resoldfor other applications. Rigid PVC (used for drinking water) is generallyfree of phthalate plasticizers although it can contain organotincompounds (e.g. dibutyltin dilauarate), which function as stabilizers.These organotin compounds can be hydrolyzed by NaOH and thenprecipitated from the reaction mixture and can be separated byfiltration. This requires a slight excess base (e.g., NaOH) in order toachieve the desired degree of dehydrochlorination, however, the reactionthen proceeds in the same manner as for the virgin PVC samples.

Thus, in specific examples disclosed are methods for partiallydehydrochlorinating PVC that comprise dissolving the PVC in an organicsolvent; and contacting the PVC with a base, thereby providing apartially dehydrochlorinated PVC. Prior to or after contacting thedissolved PVC with base, insoluble inorganic materials can be removed,e.g., by filtration or precipitation.

The disclosed method for partially dehydrochlorination of PVC can becarried out at temperatures from about room temperature to about below350° C. For example, the reaction can be carried out at temperaturesfrom room temperature to about the boiling point of the solvent used atthe pressure used. In some aspects, the reaction temperature can be fromabout 20° C. to 250° C., about 20° C. to 200° C., about 20° C. to 150°C., about 20° C. to 100° C., about 20° C. to about 60° C., from about60° to about 100° C., or from about 100° C. to about 250° C.

The partially dehydrochlorinated PVC prepared by the disclosed methodscan be from about 40% to about 95% dehydrochlorinated PVC, e.g., fromabout 60% to about 95%, from about 70% to about 95%, from about 80 toabout 95%, or from about 90 to about 95% dehydrochlorinated PVC. Theseproducts can be denoted as DHPVC_(a), where “a” is the degree ofdehydrochlorination. As an example, DHPVC₆₀ is about 60%dehydrochlorinated (about 60% of the repeating units are —CH═CH— andabout 40% of the repeating units are —CHCl—CH₂—. Thus, the disclosedmethods can be used to prepare DHPVC₅₀, DHPVC₅₅, DHPVC₆₀, DHPVC₆₅,DHPVC₇₀, DHPVC₇₅, DHPVC₈₀, DHPVC₈₅, DHPVC₉₀, and DHPVC₉₅, and any ragesof these compounds.

In specific examples, partially dehydrochlorinated PVC prepared by thedisclosed methods can have the structure

wherein x is from 1 to 1,000,000 (e.g., from 10 to 1,000,000, from 100to 1,000,000, from 1000 to 1,000,000, from 10,000 to 1,000,000, from100,000 to 1,000,000), y is from 1 to 1,000,000 (e.g., from 10 to1,000,000, from 100 to 1,000,000, from 1000 to 1,000,000, from 10,000 to1,000,000, from 100,000 to 1,000,000), and z is from 2 to 1,000,000(e.g., from 10 to 1,000,000, from 100 to 1,000,000, from 1000 to1,000,000, from 10,000 to 1,000,000, from 100,000 to 1,000,000).

The molecular weight of the DHPVC polymers prepared by the disclosedmethods can be from about 2,000 daltons to about 10,000,000 daltons, andsometimes from about 5,000 daltons to about 500,000 daltons, andsometimes from about 15,000 daltons to about 200,000 daltons.

Organic Solvent

The limited solubility of PVC in most solvents and the properties of THFmake it a suitable solvent for converting PVC to DHPVC. It is alsocontemplated herein that other organic solvents besides THF can be used,including mixtures of solvents. The organic solvent should be able todissolve PVC and generally include polar organic solvents and solventmixtures thereof. Exemplary organic solvents that can be used include,but are not limited to, tetrahydrofuran (THF), dichloromethane (DCM),chloroform (CHCl₃), acetonitrile, dimethyl sulfoxide (DMSO), pyridine,N-methylpyrrolidine (NMP), dimethylformamide (DMF), dimethylacetamide(DMA), dioxane, glycol solvents, methanol, ethanol, propanol, butanol,ethyl acetate (EtOAc), methyl ethyl ketone, acetone, and the like,including mixtures thereof. Selecting the appropriate organic solvent orsolvent mixture can be done based on the molecular weight of the PVC,the size of the PVC particles or pieces, temperature, the presence orabsence of inorganic or organic additives and plasticizers, and thelike. In specific examples, the solvent can be THF or DMF. The organicsolvent can also be heated to facilitate the dissolution of the PVC. Inother examples the solvent can be hexane or methanol, which can be usedfor heterogenous reactions.

The amount of organic solvent that can be used can vary. Generally,amounts of organic solvent that permit dissolution of the quantity ofPVC being treated should be used. Other preferences of the practitioner,e.g., easy of handling, availability, cost, etc., can be a factor inselecting the appropriate amount and type of organic solvent.

Base

The base that can be used in the disclosed methods is generally a strongbase. Exemplary bases include, but are not limited to, hydroxides,alkoxides and fluorides of the alkali metals and alkaline earth metals,carbonates, hydrogen-carbonates, phosphates, amides, silazides of thealkali metals, and combinations thereof. Particularly suitable basesinclude potassium hydroxide, sodium hydroxide, sodium carbonate,potassium carbonate, cesium carbonate, cesium phosphate, silvercarbonate, potassium tert-butoxide, sodium tert-butoxide, cesiumtert-butoxide, lithium tert-butoxide, potassium phosphate tribasic,potassium phenoxide, sodium phenoxide, a trialkyl amine, isopropoxide,and combinations thereof. In a specific example, the base can bepotassium hydroxide or sodium hydroxide.

The amount of base used in the disclosed methods can be up to 1equivalent per chlorine atom in the PVC backbone. For example, theamount of base can be from about 0.01 equivalent to about 1.5equivalents, such as from about 0.01 equivalent to about 1 equivalent,from about 0.05 equivalent to about 1 equivalent, from about 0.1equivalent to about 1 equivalent, from about 0.25 equivalent to about 1equivalent, from about 0.50 equivalent to about 1 equivalent, from about0.75 equivalent to about 1 equivalent, from about 0.9 equivalent toabout 1 equivalent, or from about 0.99 equivalent to about 1 equivalent,based on the number of chlorine atoms in the backbone.

The amount of dehydrochlorination can be controlled by the amount ofbase. For example, increasing from about 1% KOH to about 60% KOH per Clatom shows increasingly darker orange product, due to the increasingnumbers of conjugated polyene segments. Thus, in other examples, theamount of base can be from about 1% to about 100% base per Cl atom,e.g., from about 1 to about 90, about 1 to about 80, about 1 to about70, about 1 to about 60, about 1 to about 50, about 1 to about 40, about1 to about 30, about 1 to about 20, or about 1 to about 10% per Cl atom.

Non-Solvent

In further examples, the dehydrochlorinated PVC (DHPVC) can beprecipitated from the solvent and isolated, e.g., by filtration. Asuitable non-solvent is a material in which the organic solvent has highsolubility and for which the DHPVC has little or no solubility. Inaddition, the non-solvent can be chosen such that the impurities(organic and inorganic additives, plasticizers, residual base) havemoderate to high solubility. The non-solvent can be a single solvent,e.g., water, methanol, or a mixture of solvents, inter alia,methanol/water, ethanol/water. The relative compositions of solventmixtures can be adjusted by the formulator depending upon the isolationconditions. In specific examples, the non-solvent can be water,methanol, or mixtures thereof.

Methods for Hydrogenation of Partial, Dehydrochlorinated PVC

Furthermore, it is disclosed that the polyene segments in DHPVC can behydrogenated back to aliphatic hydrocarbon segments (forming H₂-DHPVC)using conditions similar to those applied in the food industry formaking saturated fats (Scheme 1). This H₂-DHPVC can then be furtherdehydrochlorinated so as to re-introduce additional polyenes. Thehydrogenation, dehydrochlorination processes can be repeated to vary ortune the levels of chloro, saturated, and unsaturated residues,providing a means to control the balance and placement of chlorinatedsegments, polyene segments and aliphatic hydrocarbon segments forming—(CH₂CHCl)_(n)—(CH═CH—)_(m)—(CH₂CH₂)_(o)— polymer backbones which arehighly tailorable to a variety of elastomer forms.

Thus, in specific examples disclosed are methods for partiallyhydrogenating a partially dehydrochlorinated PVC that comprisedissolving PVC in an organic solvent; contacting the PVC with a base,thereby providing the partially dehydrochlorinated PVC; optionallyisolating the partially dehydrochlorinated PVC; partially hydrogenatingthe partially dehydrochlorinated PVC by contacting the partiallydehydrochlorinated PVC with hydrogen in the presence of a hydrogenationcatalyst, thereby providing a partially hydrogenated, dehydrochlorinatedPVC. The partially hydrogenated, dehydrochlorinated PVC can again bedehydrochlorinated as noted herein, e.g., by dissolving the partiallyhydrogenated, dehydrochlorinated PVC in a second organic solvent andadding a second base. These second and subsequent dehydrochlorinationreactions can be performed as disclosed above using the same or adifferent organic solvent and base (that is, the second organic solventand second base can be the same as the original organic solvent andbase). As an example of this process, FIG. 1 shows comparisons of FT-IRspectra for DHPVC₆₀ and H₂-DHPVC₆₀ showing conversion of polyenesegments to saturated hydrocarbons.

The partially hydrogenated, dehydrochlorinated PVC can be from 50 to 99%hydrogenated, e.g., from about 60% to about 99%, from about 70% to about99%, from about 80 to about 99%, from about 90 to about 99%hydrogenated, from about 95 to about 99% hydrogenated or from about 98to about 99% hydrogenated. These products can be denoted asH₂-DHPVC_(b), where “b” is the degree of hydrogenation. As an example,H₂-DHPVC₆₀ is about 60% hydrogenated (i.e., about 60% of the repeatingunits are —CH₂CH₂— and about 40% are —CHCl—CH₂— and —CH═CH—). Thus, thedisclosed methods can be used to prepare H₂-DHPVC₅₀, H₂-DHPVC₅₅,H₂-DHPVC₆₀, H₂-DHPVC₆₅, H₂-DHPVC₇₀, H₂-DHPVC₇₅, H₂-DHPVC₈₀, H₂-DHPVC₈₅,H₂-DHPVC₉₀, and H₂-DHPVC₉₅, and any rages of these compounds.

In specific examples, partially hydrogenated, dehydrochlorinated PVCprepared by the disclosed methods can have the structure

wherein x is from 1 to 1,000,000 (e.g., from 10 to 1,000,000, from 100to 1,000,000, from 1000 to 1,000,000, from 10,000 to 1,000,000, from100,000 to 1,000,000), y is from 0 to 1,000,000 (e.g., from 10 to1,000,000, from 100 to 1,000,000, from 1000 to 1,000,000, from 10,000 to1,000,000, from 100,000 to 1,000,000), w is from 1 to 1,000,000 (e.g.,from 10 to 1,000,000, from 100 to 1,000,000, from 1000 to 1,000,000,from 10,000 to 1,000,000, from 100,000 to 1,000,000), and z is from 2 to1,000,000 (e.g., from 10 to 1,000,000, from 100 to 1,000,000, from 1000to 1,000,000, from 10,000 to 1,000,000, from 100,000 to 1,000,000).

The molecular weight of the H₂-DHPVC polymers prepared by the disclosedmethods can be from about 2,000 daltons to about 10,000,000 daltons, andsometimes from about 5,000 daltons to about 500,000 daltons, andsometimes from about 15,000 daltons to about 200,000 daltons.

Catalyst

Suitable reagents that can be used for hydrogenating thedehydrochlorinated PVC include hydrogen with palladium catalyst (e.g.,palladium on carbon, palladium (II) acetate, allylpalladium(II) chloridedimer, di-μ-chlorobis[(1,2,3-η)-1-phenyl-2-propenyl]dipalladium(II),cyclopentadienyl(allyl)palladium(II),cyclopentadienyl[(1,2,3-n)-1-phenyl-2-propenyl]palladium(II),palladium(II) chloride, palladium(II) pivlate, palladium(0)dba₂,palladium(II) acetylacetonate,tetrakis(triphenylphosphine)palladium(0)), hydrogen with Raney nickelcatalyst, hydrogen with Raney cobalt catalyst, lithium aluminum hydride,diisobutylaluminum hydride, and sodium borohydride.

The hydrogenation reaction can be carried out at temperatures from aboutroom temperature to about below 350° C. For example, the reaction can becarried out at temperatures from room temperature to about the boilingpoint of the solvent used at the pressure used. In some aspects, thereaction temperature can be from about 20° C. to 250° C., about 20° C.to 200° C., about 20° C. to 150° C., about 20° C. to 100° C., about 20°C. to about 60° C., from about 60° to about 100° C., or from about 100°C. to about 250° C.

Additional Modifications

The disclosed process can be used to also create DHPVC and H₂-DHPVCpolymers that can provide the appropriate backbone structures forupcycling into elastomers with desired properties and performance. DHPVCand H₂-DHPVC can be characterized via GPC, FT-IR, NMR, and/or MALDI-TOFMS to confirm the polymer backbone is still intact, and measure changesin molecular weight occurring via changes to functional groups. Also, ofinterest to the elastomeric properties is the ratio of cis- andtrans-linkages that are present in the DHPVC.

Elastomers (commonly called “rubbers”) are a class of polymers vital tothe modern economy that find use in a broad range of industrial andconsumer applications, including o-rings, gaskets, garments, andfootwear to name just a few. Elastomers are typically prepared bycrosslinking low T_(g) polymers, such as polyisoprene, polybutadiene,and chloroprene (aka Neoprene™), all of which currently rely on theproduction of new petroleum-based monomers. Unfortunately, thesecrosslinks are permanent; this is a fatal barrier to reprocessing andwhy items such as “vulcanized” car tires cannot be recycled. UsingDHPVC, two types of rubbery materials are proposed: areusable/re-moldable elastomer and a classic thermoset elastomer.

Using H₂-DHPVC (e.g., H₂-DHPVC₉₀), a reusable elastomer can be made fromthermally reversible Diels-Alder adducts between furans and maleimidesfor the crosslinks. Fully recyclable elastomeric materials based on thefuran and maleimide has been reported, including examples ofpolybutadiene and polyisoprene-based rubbers. Furan moieties can beattached to H₂-DHPVC₉₀ via simple S_(N)2 chemistry between 2-furfurylmercaptan and the residual vinyl chloride residues of H₂-DHPVC₉₀ in thepresence of a mild base (Scheme 2, top). A small amount of eliminationchemistry does occur under these conditions but should beinconsequential. Subsequent combination of the furan containingH₂-DHPVC₉₀ with a bismaleimides (featuring an alkyl linking chain), atlower temperatures, will form a crosslinked network (Scheme 2, bottom).

Below 60° C., furan/maleimides Diels-Alder adducts are stable. Attemperatures between ca. 60-100° C., an equilibrium between adductformation and dissociation exists. Above 100° C., the equilibrium shiftsso that Diels-Alder adduct dissociation dominates. This means, thatH₂-DHPVC₉₀ elastomers crosslinked by furan/bismaleimides are re-moldableand recyclable at temperatures above 100° C.

The disclosed synthetic approach to reusable H₂-DHPVC₉₀ elastomers istunable. The crosslinking density can be modified by changing furanloadings by using H₂-DHPVC with higher chlorine content. Some methodscan use simple bismaleimides linked by simple alkyl or aromatic groups,although the chain length and chain morphology can be modified. Changesin the electronics of the furan and maleimides by adding substituentscan also be used to alter both the kinetics and thermodynamics of thereversable Diels-Alder reaction, potentially increasing the usabletemperature window for crosslinked H₂-DHPVC₉₀.

Thus, in further examples, disclosed is a method that comprisescontacting the partially hydrogenated, dehydrochlorinated PVC, asdescribed herein and as prepared herein, with a nucleophile substituteddiene in the presence of a mild base, to provide a diene substitutedpartially hydrogenated dehydrochlorinated PVC; and then contacting thediene substituted partially hydrogenated dehydrochlorinated PVC with abis-dienophile.

Suitable examples of a nucleophile substituted diene are furanssubstituted with alkylthiol groups.

Suitable examples of bis-dienophiles are maleimides or azides linkedwith a linker of from 2 to 2000 atoms, e.g., an alkyl, polyalkoxyl, aryllinker, siloxane, fluoroalkyl, imidazolium, or ammonium linker. In otherexamples, the linker can be from 2 to 100 atoms, e.g., from 2 to 50, orfrom 2 to 20 atoms in length.

Chemical modifications of the polymers can be monitored by NMR and FT-IRspectroscopy. Thermal properties of H₂-DHPVC₉₀ elastomers can beexamined using conventional DSC and TGA. DMA can be used to observeelastic properties over a range of temperatures and time-dependentbehaviors (e.g., creep and relaxation). The reusability of the materialcan be assessed by observing changes in properties of the elastomer overnumerous temperature cycles; however, based on prior work onpolybutadiene furan/maleimide crosslinked systems, excellentrecyclability is expected.

The thermal-reversibility of the furan/maleimide Diels-Alder adduct,will in-part, dictate potential use of H₂-DHPVC₉₀ elastomers. Potentialapplications for recyclable H₂-DHPCV elastomers, include 3D printablerubber materials and thermal moldable elastomers. 3D printing ofelastomers is currently of great interest to many industries (e.g.,automotive, apparel, biomedical, etc.). The disclosed approach affordssimilar versatility, however by using waste PVC as a feedstock,advantages are realized with low cost starting materials and simplereactions to produce solid materials with tailored properties that canbe used in many types of 3-D printers.

Given the structural similarity of H₂-DHPVC to polyethylene, it willhave a similarly low T_(g) (<−100° C.), which is necessary to create anelastomer. If the T_(g) of H₂-DHPVC needs to be depressed, alkyl chainscan be grafted onto PVC by reacting long-chain alkyl thiols with PVC viaan S_(N)2 mechanism to lower the T_(g) of PVC. Plasticization is alsolikely to occur from the bismaleimides linked by long alkyl chains.

An important feature of H₂-DHPVC₉₀ elastomers is the low cost andsustainable nature of the chemicals necessary to synthesize it. Forexample, 2-furfuryl mercaptan is synthesized in 2 steps form furfuraland thiourea. Bismaleimides, which are key components of bismaleimide(BMI) resins, are made in one step from malic anhydride and commoditydiamines. Finally, the quantities of crosslinking agents needs is likelyonly a few weight % of the final material.

A second DHPVC-based rubber can be formed from DHPVC via classicvulcanization using elemental sulfur or zinc oxides, thiourea, etc. Andexample is shown below.

where n and m are as defined herein.

The resulting materials are traditional thermoset elastomers, withtunable properties achieved through balancing the lengths of n and m, aswell as crosslink density. While having higher temperature, stabilitycompared to reversibly crosslinked H₂-DHPVC₉₀, it will not berecyclable. The properties of DHPVC rubber will be like vulcanizedNeoprene™, given their structural similarities. If necessary, the T_(g)of DHPVC can be depressed by grafting branched alkyl chains on to thepolymer backbone by S_(N)2 chemistry.

In other examples of modifications, Scheme 3, the DHPVC can bedepolymerized by contacting the DHPVC with a metathesis catalyst and anolefin gas. The metathesis catalyst can be a homogeneous orheterogeneous catalyst. The metathesis catalyst can be an organoaluminumor organotin metathesis catalyst. The metathesis catalyst can be aGrubbs catalysts, Schrock catalyst, or second-generation Grubbscatalyst. The olefin gas can be ethylene or acetylene or propene. Inother examples of modifications, the DHPVC can be depolymerized byoxidative cleavage.

Oxidative cleavage via KMnO₄/H₃O⁺ or O₃/H₂O generatesα,ω-dialdehydes/diols (e.g., 1,4-butanediol, a key precursor to maleicanhydride) as intermediates which can then be further oxidized toα,ω-dicarboxylic acids (i.e., C_(n)H_(2(n-1))O₄). These diacids can alsobe easily converted via H⁺/MeOH to methyl ester forms which will be usedfor TPE formation. Adipic acid (C₆H₁₀O₄) is a primary target, as it hasglobal production of ˜2.5 B kg/y, primarily as a monomer for Nylon 6,6.Upcycling PVC waste to Nylon precursors represents a major opportunity,given the premium associated with Nylon, and the long lives of Nylonproducts, effectively keeping PVC waste from entering the environment.This depolymerization strategy also affords access to other diacidswhich have important uses in polymers, cleaning agents, lubricants,pharmaceuticals, and cosmetics. These larger diacids are difficult tosynthesize and/or are solely derived from plants or microorganisms. Onesuch molecule obtainable from PVC depolymerization is heneicosanedioicacid (C₂₁H₄₀O₄) a component of “Japan Wax” cosmetic formulations andcurrently sourced from trees (Rhus verniciflua, Rhus succedanea).

Olefin metathesis generates α,ω-dienes by cleaving PAA via “ethenolysis”using ethylene and an olefin metathesis catalyst (i.e., Grubbs 2^(nd)Generation). An important α,ω-diene is 1,3-butadiene, a precursor tosynthetic rubber as well as adiponitrile, another key intermediate forNylon. Other α,ω-dienes (e.g., 1,5-hexadiene, 1,8-nonadiene) findindustrial uses as precursors to a variety of chemicals.

An essential aspect of achieving high selectivity for target productsalong with narrow product distributions is controlling the size anddistributions of the PAA structures (i.e., ‘p’ and ‘m’ segments inScheme 3). While the reactions performed are well-defined, achieving theyield and selectivity targets when starting from a polymer feedstockrequires a deep understanding of the reaction mechanisms and selectionof appropriate strategies. The influence of reaction conditions will beanalyzed through systematically designed experiments that elucidate theroles of reaction variables on the formation and types of polyenestructures. These parameters include: solvent (e.g., THF, DMSO, toluene,etc.), metal hydroxide (e.g., NaOH, KOH, LiOH, etc.) or other base(e.g., K₂CO₃), temperature; solubility of the polymer backbone as itdevelops more hydrocarbon character in the transition fromDHPVC→DHPVC-H₂→PAA. Furthermore, given this potential for changes inpolymer solubility (which necessitates the use of multiple solvents), itcan be advantageous to explore strategies that form DHPVC at levels ofonly 5-10%, then cleave this DHPVC via ethenolysis (producing1,3-butadiene) such that subsequent dehydrochlorinations,hydrogenations, and cleavage reactions are performed on oligomericspecies that are more soluble in common solvents and thus easilyprocessed into final value-added products.

EXAMPLES

To further illustrate the principles of the present disclosure, thefollowing examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how thecompositions, articles, and methods claimed herein are made andevaluated. They are intended to be purely exemplary of the invention andare not intended to limit the scope of what the inventors regard astheir disclosure. Efforts have been made to ensure accuracy with respectto numbers (e.g., amounts, temperatures, etc.); however, some errors anddeviations should be accounted for. Unless indicated otherwise,temperature is ° C. or is at ambient temperature, and pressure is at ornear atmospheric. There are numerous variations and combinations ofprocess conditions that can be used to optimize product quality andperformance. Only reasonable and routine experimentation will berequired to optimize such process conditions.

DHPVC Solubility:

Experiments were conducted to determine the solubility of DHPVC in anumber of solvents. The experiments were done for DHPVC with differentdehydrochlorinated degrees (40%, 60% and 80%). All experiments were donewith the same conditions, 0.5 mg DHPVC per 1 mL of solvent (+/−0.1 mg).Table 1 summarizes the results.

TABLE 1 Solubility of DHPVC in solvents. Solvent SolubilityDimethylformamide (DMF) Soluble Dichloromethane (DCM) SolubleTetrahydrofuran (THF) Soluble Dimethylacetamide (DMA) Soluble Chloroform(CHCl3) Slightly soluble N-methylpyrrolidine (NMP) Slightly solubleotiDimethylsulfoxide (DMSO) Slightly soluble Ethyl Acetate (EtOAc)Insoluble Propylene Glycol (PG) Insoluble Dihydrolevoglucosenone(Cyrene ™) Insoluble

It was noticed that despite the solubility of DHPVC in THF, the solutionmay “gel” when left stationary or under uneven stirring. This behaviorin THF is worse with increasing dehydrochlorination degree.

Initial Dehydrochlorination (Targeted 80% removal of Cl from PVC):

PVC (10 g, 0.160 mol), KOH (7.18 g, 0.128 mol), and THF (˜650 mL) wereadded to 1 L round bottom flask. The vessel was equipped with a stir barand a reflux condenser. The reaction was heated to 65° C. and stirred atthis temperature overnight (18 h).

After this time, the reaction was allowed to cool to room temperature.Then, the contents of the vessel were poured in cold methanol, underhigh shear using a Heidolph overhead stirrer operating at 450-600 rpm.Higher shear rates help create smaller particles from the precipitatemaking it easier to dry.

The product was filtered, washed with an excess of methanol three moretimes, collected, and left to dry under vacuum. The dehydrochlorinatedPVC (“DHPVC”) product was characterized by FTIR before moving on withthe next reaction.

Hydrogenation/Saturation of Polyene Segments:

DHPVC (5 g) was added to a heavy walled 250 mL glass pressure vessel.DMF (150 mL), and 10 wt % Pd/C catalyst (0.25 g) were also added to thevessel. The vessel was sealed with a threaded PTFE cap connected to a3-way valve. Using this valve, the vessel is purged by vacuum and thenfilled with hydrogen gas at a constant pressure (˜45 psia). The reactionwas stirred at ambient temperature for 24 hours.

After this time, the Pd/C catalyst was removed via filtration throughCelite and disposed of in a safe manner. The filtrate was poured intomethanol or water under stirring. The precipitated product was collectedby vacuum filtration, then was left to dry on the filter for 24 hours.The “DHPVC-H₂” product was characterized by FTIR before moving on withthe next reaction.

Second Dehydrochlorination (Optional):

The chlorine content remaining in the DHPVC-H₂ product was calculatedwith the following equation:

$\begin{matrix}{{{Mass}\mspace{14mu}{of}\mspace{14mu}{DHPVC}} - {H\; 2(g) \times \frac{\left( {100 - {{inital}\mspace{14mu}{percentage}\mspace{14mu}{of}\mspace{14mu}{KOH}}} \right)}{100} \times \frac{1}{6{2.5}}\frac{mol}{g}}} & (1)\end{matrix}$

So, DHPVC-H₂ (2 g), KOH (0.0064 mol, 0.359 g), and 35 mL THF were addedto a 50 mL round bottom flask. The process follows the same steps as thefirst dehydrochlorination.

Heterogenous Dehydrochlorination and Hydrogenation:

Experiments were conducted to test the viability of heterogenouscondition for dehydrochlorination and hydrogenation. Dehydrochlorinationwas done by stirring 5 g of PVC and 1.28 g NaOH in 80 mL hexane under60° C. The characteristic discoloration of PVC post-dehydrochlorinationwas noticed here. This discoloration shows the potential of success forthis method.

Heterogenous hydrogenation was attempted in methanol. For this reaction,˜3 g DHPVC was stirred with 0.3 g Pd/C (10 wt %) in methanol. Thisprocess proved successful, although yields were low. This is due to thedifficulty of separating the catalyst post-hydrogenation.

Depolymerization of DHPVC:

Ethylenation reactions were experimented with in attempt to depolymerizeDHPVC. This was done by dissolving ˜2.5 g DHPVC in 120 mL DCM or THF andstirring it with 0.025 g 2nd generation Grubb's Catalyst (1 wt %) under30 psi of ethylene gas for ˜48 hrs.

The reaction media was then immediately poured into methanol todeactivate the catalyst and precipitate the product. The productproduced had a dark brown color, which is likely due to the leftovercatalyst.

Substitution of Chlorine in H-DHPVC

Attempts to substitute chlorine with imidazole (1-methylimidazolespecifically) were done. Here, 5 g PVC was dissolved in THF and mixedwith 1.28 g NaOH to make a THF/40-DHPVC solution. The solution wasfiltered to remove any unreacted base or other solid byproducts. Theproduct was left in solution for the hydrogenation reaction. Thehydrogenation was done by stirring the solution with ˜0.25 g Pd/C andput under 30 psi hydrogen gas for ˜48 hrs. Prior to the substitutionreaction, the reaction media was filtered through celite to remove thecatalyst producing a clear light-green solution. The solution was thenmixed with 2.76 g 1-methylimidazole in 150 mL acetonitrile (ACN) andheated to 80° C. overnight. After the reaction was concluded, ACN andTHF were removed by rotation evaporation producing a yellow solid. Thesolid was stirred in ether to remove any unreacted 1-methylimidazole.Although the reaction showed signs of success, the method still requiresmore optimization to increase the yield and better the processing stage.

Commercial PVC Trials

Commercial PVC was used to produce H-DHPVC. The goal of this experimentwas to determine if PVC products, like piping and packaging, needpre-treatment before going through the process of producing H-DHPVC. Forthis, 1.5 g of pipe or packaging PVC was stirred in DMF overnight toallow the solids to dissolve fully. The next day, 1.28 g NaOH was addedand left stirring for 24 hrs. The produced solution was filtered throughcelite to remove unreacted base and additives that crashed out of thesolution. The filtrate was then precipitated in methanol, filtered, anddried under reduced pressure overnight. The powder produced (0.5 g) hada light orange color and was sampled for characterization. The remainingproduct was then dissolved in DMF and mixed with 0.05 g Pd/C (10 wt %)under 30 psi hydrogen gas for ˜48 hrs. The reaction media was thenfiltered through celite to remove the catalyst. The solution was thenprecipitated in methanol, filtered, and dried under reduced pressureproducing 0.1 g of a grey powder.

FTIR spectra show that peaks belonging to potential additivesdisappearing after dehydrochlorination, giving a product that isgenerally similar to DHPVC made with lab-grade PVC.

The methods and compositions of the appended claims are not limited inscope by the specific methods and compositions described herein, whichare intended as illustrations of a few aspects of the claims and anymethods and compositions that are functionally equivalent are within thescope of this disclosure. Various modifications of the methods andcompositions in addition to those shown and described herein areintended to fall within the scope of the appended claims. Further, whileonly certain representative methods, compositions, and aspects of thesemethods and compositions are specifically described, other methods andcompositions and combinations of various features of the methods andcompositions are intended to fall within the scope of the appendedclaims, even if not specifically recited. Thus, a combination of steps,elements, components, or constituents can be explicitly mentionedherein; however, all other combinations of steps, elements, components,and constituents are included, even though not explicitly stated.

What is claimed is:
 1. A partially hydrogenated, dehydrochlorinated PVChaving the structure

wherein x is from 1 to 100,000, y is from 0 to 100,000, w is from 1 to100,000, and z is from 2 to 100,000.
 2. The partially hydrogenated,dehydrochlorinated PVC of claim 1, wherein the partially hydrogenated,dehydrochlorinated PVC is from about 50% to about 99% hydrogenated.
 3. Amethod of partially dehydrochlorinating polyvinylchloride (PVC),comprising: dissolving the PVC in an organic solvent; and contacting thePVC with a base, thereby providing a partially dehydrochlorinated PVC.4. The method of claim 3, wherein the partially dehydrochlorinated PVCis precipitated by adding a non-solvent, and the precipitate isisolated.
 5. The method of claim 3, wherein the organic solvent istetrahydrofuran, dimethylformamide, dichloromethane, dimethylacetamide,chloroform, N-methylpyrrolidine, dimethylsulfoxide, or mixtures thereof.6. The method of claim 3, wherein the base is potassium hydroxide orsodium hydroxide.
 7. The method of claim 3, wherein the non-solvent iswater, methanol, or mixtures thereof.
 8. The method of claim 3, whereinthe partially dehydrochlorinated PVC is from about 40% to about 95%dehydrochlorinated PVC.
 9. The method of claim 3, wherein the partiallydehydrochlorinated PVC has the structure

wherein x is from 1 to 1,000,000, y is from 1 to 1,000,000, and z isfrom 2 to 1,000,000.
 10. The method of claim 3, further comprisingpartially hydrogenating the partially dehydrochlorinated PVC bycontacting the partially dehydrochlorinated PVC with a hydrogenationcatalyst, thereby providing a partially hydrogenated, dehydrochlorinatedPVC.
 11. The method of claim 10, wherein the hydrogenation catalyst ishydrogen with a palladium catalyst, hydrogen with Raney nickel catalyst,hydrogen with Raney cobalt, lithium aluminum hydride, diisobutylaluminumhydride, or sodium borohydride.
 12. The method of claim 10, wherein thepartially dehydrochlorinated PVC is dissolved in a solvent and contactedwith the hydrogenation catalyst.
 13. The method of claim 10, wherein thepartially dehydrochlorinated PVC is contacted with the hydrogenationcatalyst in a non-solvent.
 14. The method of claim 10, wherein thepartially hydrogenated, dehydrochlorinated PVC is from about 50 to about99% hydrogenated.
 15. The method of claim 10, further comprisingcontacting the partially hydrogenated, dehydrochlorinated product withsulfur.
 16. The method of claim 10, wherein the partially hydrogenated,dehydrochlorinated PVC has the structure

wherein x is from 1 to 100,000, y is from 0 to 100,000, w is from 1 to100,000, and z is from 2 to 100,000.
 17. The method of claim 10, furthercomprising contacting the partially hydrogenated, dehydrochlorinated PVCwith a nucleophile substituted diene in the presence of a mild base, toprovide a diene substituted partially hydrogenated dehydrochlorinatedPVC; and contacting the diene substituted partially hydrogenateddehydrochlorinated PVC with a bis-dienophile.
 18. The method of claim17, wherein the bis-dienophile comprises two dienophiles linked via alinker having from 2 to 2000 atoms.
 19. The method of claim 10, furthercomprising dehydrochlorinating the partially hydrogenated,dehydrochlorinated PVC by dissolving the partially hydrogenated,dehydrochlorinated PVC in a second organic solvent and adding a secondbase.
 20. The method of claim 19, wherein the second organic solvent istetrahydrofuran, dimethylformamide, dichloromethane, dimethylacetamide,chloroform, N-methylpyrrolidine, dimethylsulfoxide, or mixtures thereof.21. The method of claim 16, wherein the second base is potassiumhydroxide or sodium hydroxide.
 22. The method of claim 3, wherein thetemperature is below 350° C.
 23. The method of claim 3, furthercomprising depolymerizing the partially dehydrochlorinated PVC bycontacting the partially depolymerized PVC with a metathesis catalystand olefin gas.